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摘要:
土壤环境标准样品是土壤生态环境监测质量控制的重要技术工具。目前，土壤中总有机碳环境标准样品仍为中国环境标准样品体系的空缺，特别是配套燃烧氧化-非分散红外法的土壤标准样品一直未曾问世。本文以有机碳含量较高的农用地土壤为原材料，经干燥、研磨、混匀、装瓶、灭菌等加工步骤，制备获得土壤中总有机碳环境标准样品。分层随机抽取10瓶样品进行均匀性检验，经评价统计量F小于临界值F0.05(9，10)，瓶间均匀性相对不确定度(ubb)为1.5%，样品均匀性良好。在室温避光保存条件下，对样品进行了18个月的稳定性检验，稳定性相对不确定度(ults)为1.2%，样品具有良好稳定性。由中国11家实验室采用燃烧氧化-非分散红外法和重铬酸钾容量法进行协作定值，通过对检测结果的数理统计分析，样品量值评定结果为(25.2±1.4)mg/g。该标准样品为采用燃烧氧化-非分散红外法参与定值的土壤中总有机碳环境标准样品，可作为土壤中总有机碳测定标准方法配套的实物标准，满足土壤生态环境监测及相关研究需求，且与国外同类样品具有可比性。
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关键词:
- 土壤 /
- 总有机碳 /
- 环境标准样品 /
- 标准值 /
- 燃烧氧化-非分散红外法
Abstract:BACKGROUND Soil environmental reference materials are important technical tools for the quality control of soil environmental monitoring. However, there is no self-developed environmental matrix reference material with total organic carbon (TOC). In particular, a soil standard sample supporting the combustion oxidation-non-dispersive infrared method has not been developed yet.
OBJECTIVES To develop a soil TOC reference material that can support standard methods for the determination of TOC in soil.
METHODS Agricultural land soil with a high organic carbon content was selected as the raw material. The soil TOC reference materials were prepared after drying, grinding, mixing, bottling, and sterilization. Ten bottles of the reference materials were randomly sampled in layers, and their homogeneities were determined using combustion oxidation-non-dispersive infrared (NDIR) absorption method. The data were assessed using a single element analysis of variance. The reference material was stored at room temperature, and its stability was determined for 18 months. The test results were assessed using a linear fitting model. Eleven laboratories were organized as the cooperation to determine the TOC content of the prepared reference material using combustion oxidation-NDIR absorption method and potassium dichromate volumetric method. All measurement data were statistically analyzed to obtain the certified value and uncertainty of the reference material.
RESULTS The soil TOC reference material exhibited good homogeneity and stability. After evaluation, the F value was determined to be less than the critical value of F0.05 (9, 10). Additionally, the relative uncertainty (ubb) of the uniformity between bottles was 1.5%, and the sample exhibited good uniformity. The stability uncertainty was 1.2%, which indicated good stability. The certified value of the soil TOC reference material was determined to be (25.2±1.4)mg/g, using the grand mean of the collaborative determination results from multiple laboratories.
CONCLUSIONS A soil TOC reference material was developed using combustion oxidation-NDIR absorption method. This reference material can be used to support the standard determination methods of TOC in soil and meets the requirements of the studies on TOC content in soil. Moreover, it is comparable with similar foreign samples.
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表 1 国内外主要土壤标准样品中涉及总有机碳的信息
Table 1. Information of TOC in major soil reference materials at home and abroad
土壤标准样品研制机构 土壤标准样品编号 碳含量范围(mg/g) 土壤标准样品具体类型 总碳(TC) 总有机碳(TOC) 欧盟标准样品和测量研究所 IRMM-443-1~ IRMM-443-7 14.5~108.1 13.1~59.6 欧洲土壤 美国RTC公司 RTC-CCRM090~RTC-CCRM092 - 4.13~5.72 黏土、砂壤土、砂土 RTC-SQC014 - 6.51 国家地质实验测试中心 GBW07974~GBW07977 8.1~56.8 6.9~51.5 土壤
农用地土壤GBW07913~GBW07942 6.2~79.0 3.7~47.3 中国地质科学院地球物理地球化学勘查研究所 GBW07401~GBW07408 5.5~21.1 4.9~18.0 暗棕壤、栗钙土、黄棕壤、红壤等
主要平原土壤
盐碱土、棕漠土、灰钙土、滩涂沉积物等
土壤GBW07423~GBW07430 9.3~19.0 6.2~13.5 GBW07446~GBW07457 10.3~19.4 2.5~11.5 GBW07536~GBW07573 2.8~38.1 1.7~27.5 
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表 2 土壤中总有机碳测定常用方法的比较
Table 2. Comparison of common methods for determination of TOC in soil
对比项目 燃烧氧化-非分散红外法 重铬酸钾容量法 优点 碳元素氧化完全，稳定性高，测定结果回收率高，样品前处理快捷，污染排放低 灵敏度高，操作简单，仪器设备费用低，使用成本低，更适合分析碱性土壤 缺点 仪器费用昂贵，使用维护费较高，长期使用仪器背景值易升高 存在氧化不完全的情况，易受氯离子、亚铁离子、锰化合物干扰，废液产生量大，不适合用于大量样品的快速测定 相应标准方法 《土壤有机碳的测定燃烧氧化-非分散红外法》 (HJ 695—2014) 《区域地球化学样品分析方法第27部分：有机碳量测定重铬酸钾容量法》(DZ/T 0279.27—2016)
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表 3 土壤中总有机碳标准样品的均匀性检验结果
Table 3. Homogeneity assessment results of TOC in soil reference material
样品编号 总有机碳均匀性测定结果(mg/g) RSD(%) 平行测定1 平行测定2 均值 总均值 1 24.4 22.9 23.7 23.2 1.4 2 24.0 22.6 23.3 3 23.2 23.2 23.2 4 24.5 22.6 23.6 5 24.2 23.2 23.7 6 22.5 23.5 23.0 7 23.0 23.2 23.1 8 22.2 23.3 22.8 9 22.9 22.8 22.9 10 23.4 22.9 23.2
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表 4 土壤中总有机碳标准样品的稳定性检验结果
Table 4. Stability assessment results of TOC in soil reference material
时间间隔(月) 总有机碳测定结果(mg/g) 时间间隔(月) 总有机碳测定结果(mg/g) 0 23.2 6 23.2 1 23.5 12 23.4 3 23.2 18 24.1
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表 5 协作实验室所用分析方法和测定数据
Table 5. Analysis methods and measurement data of the collaborative laboratories
实验室代号 总有机碳分析方法 总有机碳协作测定数据(mg/g) RSD(%) S-1 S-2 S-3 S-4 S-5 S-6 均值 Lab-1 燃烧氧化-非分散红外法 23.7 23.3 23.2 23.6 23.7 23.0 23.4 1.3 Lab-2 燃烧氧化-非分散红外法 23.4 22.8 22.8 23.8 22.9 22.4 23.0 2.2 Lab-3 重铬酸钾容量法 26.7 26.4 26.4 26.3 26.5 26.4 26.5 0.6 Lab-4a 重铬酸钾容量法 25.4 25.6 26.1 26.0 26.0 25.4 25.8 1.3 Lab-4b 燃烧氧化-非分散红外法 25.9 25.9 25.5 25.7 25.7 26.1 25.8 0.9 Lab-5 重铬酸钾容量法 26.3 24.7 25.1 27.8 26.7 27.3 26.3 4.7 Lab-6 重铬酸钾容量法 25.8 26.3 26.5 25.9 26.3 26.0 26.1 1.1 Lab-7 重铬酸钾容量法 25.2 25.3 25.4 25.3 25.2 25.0 25.2 0.6 Lab-8 燃烧氧化-非分散红外法 21.1 21.1 21.5 21.1 21.3 21.3 21.2 0.8 Lab-9 重铬酸钾容量法 27.1 27.1 28.1 28.4 28.2 28.2 27.9 2.2 Lab-10 重铬酸钾容量法 26.1 26.0 25.4 26.3 24.9 26.0 25.8 2.1 Lab-11 燃烧氧化-非分散红外法 24.9 24.8 25.4 25.4 25.1 25.7 25.2 1.4
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